JP2020527623A - Flame-retardant black polyamide compositions and their use - Google Patents

Abstract

Summary Black flame-retardant polyamide compositions and their use. The present invention relates to a flame-retardant polyamide composition comprising: as component A, a polyamide having a melting point of 290 ° C. or lower, as component B, a filler and / or a reinforcing material, and as component C, phosphinic acid of the formula (I). Salt [In the formula, R1 and R2 represent ethyl, M is Al, Fe, TiOp or Zn, m represents 2 or more and less than 4, and p = (4-m) / 2]. , A group of Al-, Fe-, TiOp- or Zn salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexyl-phosphinic acid, butylhexylphosphinic acid and / or dihexylphosphinic acid as component D. As the compound selected from the components E, the phosphonate of the formula II [in the formula, R3 represents ethyl, Met is Al, Fe, TiOq or Zn, and n represents 2 or more and less than 4. And q = (4-n) / 2], a melamine polyphosphate having an average degree of condensation of 2 to 200 as the component F, and a black colorant as the component G. The black polyamide composition can be used for the production of fibers, films and moldings, especially fibers, films and moldings for use in the electrical and electronic fields.

Description

The present invention relates to flame-retardant polyamide compositions and molded articles made from them.

Flammable plastics must typically be finished with flame retardants in order to meet the high flame retardancy requirements of plastic processors and, in some cases, legislators. Preferably-for ecological reasons-a non-halogenated flame retardant system is used that produces little or no smoke gas.

Among these flame retardants, salts of phosphinic acids (phosphinates) have been found to be particularly effective against thermoplastic polymers (DE2252258A (Patent Document 1) and DE24477727A (Patent Document 2)).

In addition, synergistic combinations of phosphinates with specific nitrogen-containing compounds are known to act more effectively as flame retardants than phosphinate alone in all series of polymers (WO-2002 / 28953A1 (Patent Document 3)). DE197344437A1 (Patent Document 4) and DE197377727A1 (Patent Document 5)).

From US7,420,007B2 (Patent Document 6), it is known that a dialkylphosphinate containing a small amount of selected telomer is suitable as a flame retardant for a polymer, and the polymer is a polymer of the flame retardant. Incorporation into the matrix undergoes very little degradation.

Flame retardants must often be added in high doses to ensure sufficient flame retardancy of plastics according to international standards. Due to their chemical reactivity required for flame retardant action at high temperatures, flame retardants can impair the processing stability of plastics, especially at higher doses. Increased polymer degradation, cross-linking reactions, degassing or discoloration can occur.

From WO2014 / 135256A1 (Patent Document 7), polyamide molding materials with significantly improved thermal stability, reduced migration tendency, and good electrical and mechanical properties are known.

Polyamide compositions colored black have also already been described. DE19925221A1 (Patent Document 8) discloses a reinforced polyamide resin composition colored with carbon black and selected copper phthalocyanine. From WO2010 / 089241A1 (Patent Document 9), a thermoplastic molding material containing a gray or black colorant in addition to a fibrous filler colored in gray or black is known. This document states that polyamide can also be used as a thermoplastic.

When red phosphorus as a flame retardant, or a combination of halogen-containing aromatics and antimony trioxide, and commonly used black pigments or dyes are used, the black coloration of the molding material and the molded product is not desirable. It was found to be tinged with.

However, to date, all required properties, such as good electrical values (CTI, GWFI), deep black tint (color) and as short a residual flame time as possible (UL-94, time) have been characterized by effectiveness. There was no flame-retardant phosphinate-containing polyamide composition that simultaneously achieved high flame retardancy.

DE2252258A DE24477727A WO-2002 / 28953A1 DE197344437A1 DE197377727A1 US7,420,007B2 WO2014 / 135256A1 DE19922521A1 WO2010 / 089241A1

Therefore, the subject of the present invention is based on a phosphinate-containing flame retardant system which has all of the above properties at the same time and is highly flame retardant, particularly characterized by a deep black color and the shortest possible residual flame time. It was to provide a flame-retardant polyamide composition.

The subject of the present invention is a flame-retardant polyamide composition comprising:
-As component A, a polyamide having a melting point of 290 ° C. or lower, preferably 280 ° C. or lower, particularly preferably 250 ° C. or lower.
-As component B, filler and / or reinforcing material, preferably glass fiber,
-As component C, the phosphinate of formula (I)

［式中、Ｒ_１およびＲ_２は、エチルを表し、
Ｍは、Ａｌ、Ｆｅ、ＴｉＯ_ｐまたはＺｎであり、
ｍは、２〜３、好ましくは２または３を表し、そして
ｐ ＝（４ −ｍ）／２である］、
− 成分Ｄとして、エチルブチルホスフィン酸の、ジブチルホスフィン酸の、エチルへキシルホスフィン酸の、ブチルへキシルホスフィン酸のおよび／またはジヘキシルホスフィン酸のＡｌ−、Ｆｅ−、ＴｉＯ_ｐ−またはＺｎ塩の群から選択される化合物、
− 成分Ｅとして、式ＩＩのホスホン酸塩

[In the formula, R ₁ and R ₂ represent ethyl and
M is Al, Fe, TiO _p or Zn,
m represents 2-3, preferably 2 or 3, and p = (4-m) / 2],
-A group of Al-, Fe-, TiO _p- or Zn salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and / or dihexylphosphinic acid as component D. Compounds selected from,
-As component E, the phosphonate of formula II

［式中、Ｒ_３は、エチルを表し、
Ｍｅｔは、Ａｌ、Ｆｅ、ＴｉＯ_ｑまたはＺｎであり、
ｎは、２〜３、好ましくは２または３を表し、そして
ｑ ＝（４−ｎ）／２である］、
− 成分Ｆとして、２〜２００の平均縮合度を有するメラミンポリホスフェート、および
− 成分Ｇとして、黒色の着色剤。

[In the formula, R ₃ represents ethyl and
Met is Al, Fe, TiO _q or Zn.
n represents 2-3, preferably 2 or 3, and q = (4-n) / 2],
-As component F, melamine polyphosphate having an average degree of condensation of 2 to 200, and-as component G, a black colorant.

In the polyamide composition of the present invention, the proportion of component A is usually 25 to 95% by weight, preferably 25 to 75% by weight.

In the polyamide composition of the present invention, the proportion of component B is usually 1 to 45% by weight, preferably 20 to 40% by weight.

In the polyamide composition of the present invention, the proportion of component C is usually 1 to 35% by weight, preferably 5 to 20% by weight.

In the polyamide composition of the present invention, the proportion of component D is usually 0.01 to 3% by weight, preferably 0.05 to 1.5% by weight.

In the polyamide composition of the present invention, the proportion of component E is usually 0.001 to 1% by weight, preferably 0.01 to 0.6% by weight.

In the polyamide composition of the present invention, the proportion of component F is usually 1 to 25% by weight, preferably 2 to 10% by weight.

In the polyamide composition of the present invention, the proportion of component G is usually 0.01 to 20% by weight, preferably 0.01 to 10% by weight, and particularly 0.1 to 8% by weight.

Here, the percentage display regarding the ratio of the components A to G is based on the total amount of the polyamide composition.

-The ratio of component A is 25 to 95% by weight,
-The ratio of component B is 1 to 45% by weight,
-The ratio of component C is 1 to 35% by weight,
-The ratio of component D is 0.01 to 3% by weight.
-The ratio of component E is 0.001 to 1% by weight.
-The proportion of component F is 1 to 25% by weight, and-the proportion of component G is 0.01 to 20% by weight (the percentage representation is based on the total amount of the polyamide composition).
A flame-retardant polyamide composition is preferred.

-The ratio of component A is 25 to 75% by weight,
-The ratio of component B is 20-40% by weight,
-The ratio of component C is 5 to 20% by weight,
-The ratio of component D is 0.05 to 1.5% by weight.
-The ratio of component E is 0.01 to 0.6% by weight.
-The proportion of component F is 2-10% by weight, and-the proportion of component G is 0.1-8% by weight (the percentage indication is based on the total amount of the polyamide composition).
Flame-retardant polyamide compositions are particularly preferred.

A preferably used salt of component C is a salt in which M ^{m +} represents Zn ²⁺ , Fe ³⁺ or particularly Al ³⁺ .

Preferred used salts of component D are zinc-, iron- or especially aluminum salts.

A preferably used salt of component E is a salt in which Met ^{n +} represents Zn ²⁺ , Fe ³⁺ or particularly Al ³⁺ .

A flame-retardant polyamide composition in which M and Met represent Al, m and n are 3, and the compound of component D is present as an aluminum salt is particularly highly preferred.

In a preferred embodiment, the flame-retardant polyamide composition described above comprises an inorganic phosphonate as yet another component H.

The use of the inorganic phosphonate or the salt of phosphorous acid (phosphite) used as the component H in the present invention as a flame retardant is known. For example, WO2012 / 0454414A1 discloses a flame retardant combination containing a salt of phosphorous acid (= phosphite) in addition to phosphate.

Preferably, the inorganic phosphonate (component H) follows the general formula (IV) or (V) [(HO) PO ₂ ] ^2- _{p / 2} Kat ^{p +} (IV).
[(HO) ₂ PO] ⁻ _p Kat ^{p +} (V)
[In the formula, Kat is a p-valent cation, especially an alkali metal, an alkaline earth metal cation, an ammonium cation, and / or a Fe, Zn cation, or especially an Al cation (cation Al (OH) or Al (OH). ) Including ₂ ), and p represents 1, 2, 3 or 4].

Preferably, the inorganic phosphonate (component H) is aluminum phosphite [Al (H ₂ PO ₃ ) ₃ ], secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], basic aluminum phosphite [Al ( OH) (H ₂ PO ₃ ) ₂ * 2aq], aluminum phosphite tetrahydrate [Al ₂ (HPO ₃ ) ₃ * 4aq], aluminum phosphonate, Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1,6) - is _{hexanediamine) 1.5 * 12H 2 O, Al} 2 (HPO 3) 3 * xAl 2 O 3 * nH 2 O (x = 2.27~1) and / or _Al 4 _H 6 _P 16 _{O 18} ..

The inorganic phosphonate (component H) is preferably also an aluminum phosphite of the formulas (VI), (VII) and / or (VIII) Al ₂ (HPO ₃ ) ₃ x (H ₂ O) _q (VI).
(In the formula, q represents 0-4);
Al _2.00 M _z (HPO ₃ ) _y (OH) _v x (H ₂ O) _w (VII),
(In the formula, M represents an alkali metal cation, z represents 0.01-1.5, y represents 2.63-3.5, v represents 0-2, and w represents 0-4);
Al _2.00 (HPO ₃ ) _u (H ₂ PO ₃ ) _t x (H ₂ O) _s (VIII),
(In the formula, u represents 2 to 2.99, t represents 2 to 0.01, and s represents 0 to 4)
And
And / or aluminum phosphite [Al (H2PO ₃ ) ₃ ], secondary aluminum phosphite [Al ₂ (HPO ₃ ) ₃ ], basic aluminum phosphite [Al (OH) (H ₂ PO ₃ ) ₂ * 2aq] , Aluminum phosphite tetrahydrate [Al ₂ (HPO ₃ ) ₃ * 4aq], Aluminum phosphonate, Al ₇ (HPO ₃ ) ₉ (OH) ₆ (1,6-hexanediamine) _1.5 * 12H ₂ O, Al ₂ (HPO ₃ ) ³ * xAl ₂ O ₃ * nH ₂ O (x = 2.27-1) and / or Al ₄ H ₆ P ₁₆ O ₁₈ .

A preferred inorganic phosphonate (component H) is a salt that is insoluble or sparingly soluble in water.

Particularly preferred inorganic phosphonates are aluminum-, calcium- and zinc salts.

Particularly preferably, component H is a reaction product from a phosphorous acid and an aluminum compound.

Particularly preferred components H are CAS numbers 15099-32-8, 119103-85-4, 220689-59-8, 56287-23-1, 156024-71-4, 71449-76-8 and 15099-32-8. It is an aluminum phosphite having.

The production of the preferably used aluminum phosphite is carried out by reacting the aluminum source with the phosphorus source and optionally the template in a solvent at 20-200 ° C. for a period of up to 4 days. To do this, the aluminum and phosphorus sources are mixed for 1-4 hours, heated under hot water conditions or under reflux, filtered, washed and dried, for example at 110 ° C.

Preferred aluminum sources are aluminum isopropoxide, aluminum nitrate, aluminum chloride and aluminum hydroxide (eg pseudo-bemite).

Preferred phosphorus sources are phosphorous acid, (acidic) ammonium phosphite, alkali metal phosphite or alkaline earth metal phosphite.

Preferred alkali metal phosphite is disodium phosphite, disodium phosphite hydrate, trisodium phosphite, potassium hydrogen phosphite.

Preferred phosphite disodium hydrate, Brueggemann's Brueggolen ^{(registered trademark)} is H10.

Preferred templates are 1,6-hexanediamine, guanidine carbonate or ammonia.

A preferred alkaline earth metal phosphite is calcium phosphite.

Here, the preferable ratio of aluminum, phosphorus and solvent is 1: 1: 3.7 to 1: 2.2: 100 mol. The ratio of aluminum to the template is 1: 0 to 1:17 mol. The preferred pH value of the reaction solution is 3-9. The preferred solvent is water.

Particularly preferably, in the above use, the same salts of phosphinic acid as in the case of phosphates, eg, aluminum diethylphosphite, with aluminum phosphite, or zinc diethylphosphite with zinc phosphate. used.

In a preferred embodiment, the flame-retardant polyester composition comprises the compound of formula (III) as component H.

［式中、Ｍｅは、Ｆｅ、ＴｉＯ_ｒ、Ｚｎ、または特にＡｌであり、
ｏは、２〜３、好ましくは２または３を表し、そして
ｒ＝（４−ｏ）／２である］。

[In the formulas, Me, Fe, a _TiO r, Zn or especially Al,,
o represents 2-3, preferably 2 or 3, and r = (4-o) / 2].

A preferably used compound of formula III is a compound in which ^{Meo +} represents Zn ²⁺ , Fe ³⁺ or in particular Al ³⁺ .

The component H is preferably present in an amount of 0.005 to 10% by weight, particularly 0.02 to 5% by weight, based on the total amount of the polyamide composition.

Preferably, the flame-retardant polyamide composition of the present invention has a comparative tracking index of 500 volts or more measured according to the International Electrotechnical Commission standard IEC-60112 / 3.

Similarly, preferred flame-retardant polyamide compositions of the present invention achieve a V0 rating by UL-94, especially measured on molded articles with a thickness of 3.2 mm to 0.4 mm.

A further preferred flame-retardant polyamide composition of the present invention has a glow wire flammability index according to IEC-60695-2-12 at least 960 ° C., especially measured in moldings with a thickness of 0.75-3 mm.

The polyamide composition of the present invention contains one or more kinds of polyamides having a melting point of 290 ° C. or lower as component A. Here, the melting point is measured at a heating rate of 10 K / sec using differential scanning calorimetry (DSC).

Polyamides of component A are generally derived from (cyclo) aliphatic dicarboxylic acids or polyamide-forming derivatives thereof, such as salts thereof, or (cyclo) aliphatic diamines or (cyclo) aliphatic aminocarboxylic acids or them. Polyamide-forming derivatives of, eg, aliphatic homo- or copolyamides derived from salts thereof.

The polyamide used as component A in the present invention is a thermoplastic polyamide.

Thermoplastic polyamides have no side chains or some molecular chains, based on Hans Domininghaus's "Die Kunststoffe und ifre Eignschaften (Plastics and Their Properties)", 5th Edition (1998), page 14. It is understood to be a polyamide that has various amounts of side chains of various lengths, softens when heated, and can be molded almost arbitrarily.

The polyamide used as component A in the present invention can be produced according to various methods, can be synthesized from various components, and in a specific application, alone or as a processing aid, stabilizer. Alternatively, it can be further combined with a polymer alloy partner, preferably an elastomer, to finish the material with a particular established property combination. Mixtures with some other polymer, preferably polyethylene, polypropylene, ABS are also suitable, where one or more compatibles can optionally be used. The properties of the polyamide can be improved by the addition of the elastomer, for example with respect to impact strength, especially when the polyamide is a glass fiber reinforced polyamide as described herein. The many possible combinations allow for a large number of products with different properties.

Numerous methods are known for the production of polyamides, in which different monomer constituent units, different chain modifiers for the regulation of the molecular weight of the target, or subsequent, depending on the desired final product. Monomers with reactive groups for the intended post-treatment of are also used.

Industrially related methods for the production of polyamides usually proceed through polycondensation in the melt. In this series, hydrolytic polymerization of lactams is also understood as polycondensation.

Preferably, the polyamides to be used as component A are semi-crystalline aliphatic polyamides, aliphatic diamines and aliphatic dicarboxylic acids having at least 5 ring members and / or alicyclic lactams, or corresponding It is a semi-crystalline aliphatic polyamide that can be produced starting from the amino acids of.

As starting materials, aliphatic dicarboxylic acids, preferably adipic acid, 2,2,4- and 2,4,4-trimethyladipic acid, azelaic acid and / or sebacic acid, aliphatic diamines, preferably tetramethylenediamine, Hexamethylenediamine, 1,9-nonanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, isomers of diaminodicyclohexylmethane, diaminodicyclohexylpropane, bisaminomethylcyclohexane, aminocarboxylic acid, preferably Aminocaproic acid or the corresponding lactams are possible. Copolyamides from a plurality of the above monomers are included. Particularly preferably caprolactam, particularly very preferably ε-caprolactam is used.

Preferably, the aliphatic homo- or copolyamide used in the present invention is polyamide 12, polyamide 4, polyamide 4, 6, polyamide 6, polyamide 6, 6, polyamide 6, 9, polyamide 6, 10, polyamide 6, 12, Polyamide 6, 66, Polyamide 7, 7, Polyamide 8, 8, Polyamide 9, 9, Polyamide 10, 9, Polyamide 10, 10, Polyamide 11 or Polyamide 12. These are, for example, the trademarks Nylon ^{(registered trademark)} (DuPont), Ultramid ^{(registered trademark)} (BASF), Akulon ^{(registered trademark)} K122 (DSM), Zytel ^{(registered trademark)} 7301 (DuPont); Durethan ^(registered ). known in the ^trade) B29 (Bayer Co., Ltd.) and Grillamid ^{(registered trademark)} (Ems Chemie Co., Ltd.).

In particular, compounds based on PA6, PA6, 6 and other aliphatic homo- or copolyamides are more suitable, in which there are 3-11 methylene groups per polyamide group in the polymer chain.

A flame-retardant polyamide composition in which one or more polyamides selected from the group consisting of PA6, PA6,6, PA4,6, PA12, PA6, 10 is used as component A is preferable.

A flame-retardant polyamide composition in which a polyamide 6,6 or a polymer mixture of polyamides 6,6 and polyamide 6 is used as the component A is particularly preferable.

A flame-retardant polyamide composition consisting of polyamides 6 and 6 having a component A of at least 75% and polyamide 6 having a maximum component A of 25% by weight is particularly highly preferred.

As the component B, a filler and / or preferably a reinforcing material, preferably glass fiber is used. Mixtures of two or more different fillers and / or reinforcements can also be used.

Preferred fillers are talc, mica, silicate, quartz, titanium dioxide, silicate stone, kaolin, amorphous silica, nanoscale minerals, especially preferably montmorillonite or nanobemite, magnesium carbonate, barium, feldspar, glass sphere and / Alternatively, it is a mineral particulate filler based on barium sulfate. Particularly preferably, the mineral particulate filler is based on talc, wollastonite and / or kaolin.

Further, particularly preferably, acicular mineral fillers can also be used. Needle-like mineral fillers are understood in the present invention as mineral-based fillers having very pronounced needle-like properties. Needle wollastonite is preferred. Preferably, the minerals have a length-to-diameter ratio of 2: 1 to 35: 1, particularly preferably 3: 1 to 19: 1, and particularly preferably 4: 1 to 12: 1. The average particle size of the needle-like mineral filler used as the component B in the present invention is preferably less than 20 μm, particularly preferably less than 15 μm, and particularly preferably less than 10 μm when measured with a CILAS particle size meter.

The component B preferably used in the present invention is a reinforcing material. Here, for example, a reinforcing material based on carbon fiber and / or glass fiber can be mentioned.

In a preferred embodiment, the filler and / or the reinforcing material may be surface-modified, preferably using an adhesion promoter or an adhesion promoter system (particularly preferably silane-based). May be good. In particular, when glass fibers are used, in addition to silanes, polymer dispersions, film forming agents, branching agents and / or glass fiber processing aids can also be used.

The glass fibers preferably used as the component B in the present invention may be short glass fibers and / or long glass fibers. Chopped fibers can be used as the short glass fibers or the long glass fibers. Short glass fibers can also be used in the form of milled glass fibers. In addition, fiberglass can also be used in the form of continuous fibers, eg in the form of roving, monofilament, filament yarn or twisted yarn, or fiberglass in the form of textiles, eg as glass cloth, as glass braid. Or it can be used as a glass mat.

Typical fiber lengths of short glass fibers prior to incorporation into the polyamide matrix range from 0.05 to 10 mm, preferably 0.1 to 5 mm. After incorporation into the polyamide matrix, the length of the glass fibers decreased. The typical fiber length of the glass short fibers after incorporation into the polyamide matrix is in the range of 0.01 to 2 mm, preferably 0.02 to 1 mm.

The diameter of individual fibers can vary over a wide range. The typical diameter of individual fibers can vary in the range of 5-20 μm.

The glass fiber can have any cross-sectional shape, eg, circular, oval, n-sided or irregular cross-section. Glass fibers having a mono-ordor multilobalen cross section may be used.

The glass fiber may be used as a continuous fiber or as a cut or crushed glass fiber.

The glass fibers themselves are, for example, E-glass fiber, A-glass fiber, C-glass fiber, D-glass fiber, M-glass fiber, S-glass fiber, R-, regardless of their cross-sectional area and length. It can be selected from the group of fiberglass and / or ECR fiberglass, with E-glass fiber, R-glass fiber, S-glass fiber and ECR glass fiber being particularly preferred. The glass fibers are preferably provided in a size that preferably contains polyurethane as a film-forming agent and aminosilane as an adhesion promoter.

Particularly E- glass fibers used preferably have the following chemical _{composition: SiO 2 50-56%; Al 2} O 3 12-16%; CaO 16-25%; MgO ≦ 6%; B 2 O 3 6 -13%; F ≤ 0.7%; Na ₂ O 0.3-2%; K ₂ O 0.2-0.5%; Fe ₂ O ₃ 0.3%.

Particularly preferably used R-glass fibers have the following chemical composition: SiO ₂ 50-65%; Al ₂ O ₃ 20-30%; CaO 6-16%; MgO 5-20%; Na ₂ O 0 .3-0.5%; K ₂ O 0.05-0.2%; Fe ₂ O ₃ 0.2-0.4%, TiO ₂ 0.1-0.3%.

Particularly preferably used ECR-glass fibers have the following chemical composition: SiO ₂ 57.5-58.5%; Al ₂ O ₃ 17.5-19.0%; CaO 11.5-13.0 %; MgO 9.5-11.5.

The salt of diethylphosphinic acid used as component C in the present invention is a known flame retardant for polymer molding materials.

A salt of diethylphosphinic acid containing a small amount of phosphinic acid- and a phosphonate used as components D and E in the present invention is also a known flame retardant. The production of combinations of these substances is described, for example, in US 7,420,007B2.

The diethylphosphinic acid salt of the component C used in the present invention may contain a small amount of the salt of the component D and the salt of the component E, for example, based on the amount of the components C, D and E, for example, 10. Component D up to% by weight, preferably 0.01-6% by weight, especially 0.2-2.5% by weight D, and component E up to 10% by weight, preferably 0.01-6% by weight, especially. It may contain 0.2 to 2.5% by weight of component E.

The salt of ethylphosphonic acid used as component E in the present invention is also known from, for example, WO2016 / 065971A1 as an additive to diethyl phosphinate in flame retardants for polymer molding materials.

The use of a polyphosphate derivative of melamine having a degree of condensation of 20 or more used as the component F in the present invention as a flame retardant is also known. For example, DE102005016195A1 discloses a stabilized flame retardant containing 99-1% by weight melamine polyphosphate and 1-99% by weight additive with preliminary alkalinity. The literature also discloses that the flame retardant can be combined with phosphinic acid and / or phosphinate.

The preferred flame-retardant polyamide composition of the present invention contains, as component F, melamine polyphosphate having an average degree of condensation of 20 to 200, particularly 40 to 150.

In another preferred range, the average degree of condensation is about 2-100.

A more preferable flame-retardant polyamide composition of the present invention contains as component F melamine polyphosphate having a decomposition temperature of 320 ° C. or higher, particularly 360 ° C. or higher, particularly preferably 400 ° C. or higher.

Preferably, as the component F, melamine polyphosphates known from WO2006 / 027340A1 (corresponding to EP1789475B1) and WO2000 / 002869A1 (corresponding to EP1095030B1) are used.

Preferably, it is a melamine polyphosphate having an average degree of condensation of 20 to 200, particularly 40 to 150, and a melamine content of 1.1 to 2.0 mol per 1 mol of phosphorus atoms, particularly 1.2 to 1.8 mol. Melamine polyphosphates are used.

Similarly preferably, melamine polyphosphates have an average degree of condensation (number average molecular weight) of> 20, a decomposition temperature of more than 320 ° C., and a molar ratio of 1,3,5-triazine compound to phosphorus. Melamine polyphosphate having a pH value of less than 1.1, particularly 0.8 to 1.0, and a suspension having a 10% concentration in water at 25 ° C. of 5 or more, preferably 5.1 to 6.9. Kind is used.

In a further preferred embodiment, the components C, D, E and F are present in particulate form with a median particle size (d ₅₀ ) of 1-100 μm.

As component G, the polyamide composition of the present invention contains one or more black colorants.

Colorants are generally understood as all colorants according to DIN ISO 18451, which can be classified as inorganic and organic colorants, as well as natural and synthetic colorants (Roempps Chemie Lexicon, 1981, 8th edition, See p.1237).

Dyes and pigments are distinguished according to DIN ISO 18451, where the latter is insoluble in plastics and the dyes are soluble.

Dyes and pigments that can be preferably used as component G include carbon black, graphite, graphene, niglocin, bone charcoal, black coloring pigments, or a combination of complementary colors from red to yellow and green, blue or purple pigments. Alternatively, one or more mixtures of these compounds may be mentioned.

Suitable carbon blacks as component G include, in particular, carbon blacks having a pore volume (DBP dibutyl phthalate adsorption) according to DIN ISO 18451 of at least 30 ml / 100 g, preferably at least 50 ml / 100 g.

Further carbon blacks preferably used as component G have a BET specific surface area (according to ISO 4652) of at least 20-1000 m ² / g, preferably 30-300 m ² / g.

Further carbon blacks preferably used as component G have an average primary particle size of 5 to 50 nm, especially 10 to 35 nm.

These types of carbon black, for example, Printex ^{(registered trademark)} XE2 under the trademark (Evonik GmbH), or as Ketjenblack ^(R) EC 600JD (Akzo), and furnace black, for example, Printex ^{(registered trademark)} 90, It is available as 75, 80, 85, 95 and 60-A.

In addition, graphite can also be used as component G. It can be refined by milling. The particle size is usually in the range of 0.01 μm to 1 mm, preferably in the range of 1 to 250 μm. Graphite is very soft (Mohs hardness 1) and has an inherent grayish to black color.

A further example of a blackening agent suitable as component G is graphene. Commercial graphene is, for example, Vor-x ^(TM) products (Vorbeck Materials). Graphene usually has a thickness of 1 to 5 nm, a diameter of 20 to 1000 nm, and a BET specific surface area of 500 to 1000 mm ² / g (N ₂ ).

Preferably, the blackening agent used as component G is niglosin. This is generally understood in various embodiments as a group of black or gray phenazine dyes (azine dyes) associated with indurin. Nigrosin can be water-soluble, fat-soluble or alcohol-soluble. Industrially, niglosin is obtained by heating nitrobenzene, aniline and aniline hydrochloride with metallic iron and FeCl ₃ .

Niglosin can be used as a free base or as a salt (eg, as a hydrochloride).

In addition, bone charcoal or animal black (Knochenschwarz) can be used as component G. Bone charcoal can be produced by heating defatted ground bone to about 700 ° C. under air barrier. Carbonization with concentrated sulfuric acid from a mixture of bone charcoal with sugar or syrup results in so-called animal black or Coelner Schwarz. The finely ground bone charcoal is suitable for coloring thermoplastic molding materials. Denatured bone charcoal can also be used as component G. For example, squeezing the mineral components from the bone charcoal with hydrochloric acid leaves a darker bone charcoal, which is available as Blacklake (Lackschwarz) or Paris Black (Pariser Schwarz) mixed with a small amount of Berlin blue.

Suitable colorants that can be used as component G are generally classified by color index (C. l.), and in addition to the systematic name or common name, C.I. I. The name is added.

Black coloring pigments that can be used as component G in the present invention include, for example, iron oxide black (Fe ₃ O ₄ ), spinel black (Cu, (Cr, Fe) ₂ O ₄ ), manganese black (manganese dioxide, silicon dioxide and A mixture of iron oxides), cobalt black or antimon black.

In addition, complementary color pigments can be used to achieve the black color of the polyamide compositions of the present invention.

To this end, red to yellow pigments are used with the corresponding complementary green, blue or purple pigments or mixtures thereof to achieve the black color of the polyamide composition as desired.

Preferred pigments include copper phthalocyanine pigments having a green or blue color. The green color is generally obtained by the substitution of hydrogen by chlorine atoms on the macrocyclic tetraamine.

Yet another suitable pigment is a manganese violet pigment, a pyrophosphate consisting of ammonium and manganese (III) of formula MnNH ₄ P ₂ O ₇ , which gives a bluer or reddish tint depending on the variation in chemical composition. ), Ultramarine pigments (sodium silicate, aluminum silicate), eg, blue and green pigments based on chromium oxide or cobalt oxide with a spinel structure. Such pigments, trade names Heliogen ^{(registered trademark)} blue, Heliogen ^{(registered trademark)} - green, Sicopal ^{(registered trademark)} - green, Sicopal ^{(registered trademark)} - Blue (trademark of BASF SE), and ultramarine, It is commercially available as a chromium oxide-or manganese violet pigment.

Preferred pigments are C.I. I. According to Part 1, Pigment Blue 15, Pigment Blue 15: 2, Pigment Blue 15: 4, Pigment Blue 16, Pigment Blue 28, Pigment Blue 29, Pigment Blue 36, Pigment Green 17, Pigment Green 24, Pigment Green 50, Pigment Violet 15 and Pigment Violet 16, where Pigment Blue 15: 1 and 15: 3 and Pigment Greens 7 and 36 are particularly preferred.

Preferably, the component G is carbon black, graphite, graphene, niglocin, bone charcoal, a black coloring pigment, or a combination of a complementary color from red to yellow and a green, blue or purple pigment, or a compound thereof. A black pigment or dye selected from the group of one or more mixtures.

Polyamide compositions according to the invention preferably have a black color characterized by RAL color chart numbers 9004, 9005, 9011, 9017 and 9021, in particular by RAL9005 ("Jet black" (Tiefschwarz)).

The polyamide composition according to the present invention may also contain yet another additive as component I. In the sense of the present invention, the preferred component I is an antioxidant, a UV stabilizer, a gamma ray stabilizer, a hydrolysis stabilizer, a co-stabilizer for antioxidants, an antistatic agent, an emulsifier, a nucleating agent, a softening agent. , Processing aids, impact resistance improvers, dyes different from component G, pigments different from component G and / or yet another flame retardant different from components C, D, E, F and H.

These include, in particular, phosphates, melamine poly (metal phosphate). Preferred metals in this regard are the elements of the 2nd, 3rd, 2nd, 4th and VIIIa groups of the periodic table, and cerium and / or lanthanum.

The melamine-poly (metal phosphate) is preferably melamine-poly (zinc phosphate), melamine-poly (magnesium phosphate) and / or melamine-poly (calcium phosphate).

(Melamine) ₂ Mg (HPO ₄ ) ₂ , (Melamine) ₂ Ca (HPO ₄ ) ₂ , (Melamine) ₂ Zn (HPO4) ₂ , (Melamine) ₃ Al (HPO ₄ ) ₃ , (Melamine) ₂ Mg (P) ₂ O ₇ ), (melamine) ₂ Ca (P ₂ O ₇ ), (melamine) ₂ Zn (P ₂ O ₇ ), (melamine) ₃ Al (P ₂ O ₇ ) _3/2 are preferable.

Known as hydrogen phosphato- or pyrophosphatometallate having a complex anion, melamine poly (metal phosphate) having a 4- or 6-bonding metal atom as a bidentate hydrogen phosphate-or pyrophosphate-ligand is preferred. ..

Aluminum-, zinc- or magnesium salts of condensed phosphates with melamine inserted are also preferred, bis-melamine-zinco-diphosphate and / or bis-melamine-aluminotriphosphate (Bis). -Melamine-aluminum phoshat) is particularly highly preferred.

In addition, with the elements of the 2nd, 3rd, 2nd, 4th and VIIIa groups of the periodic table, and the anion of the 5th main group oxoacid of cerium and / or lanthanum. Salts (phosphate, pyrophosphate and polyphosphate) are preferred.

Aluminum phosphate, aluminum monophosphate; aluminum orthophosphate (AlPO ₄ ), aluminum hydrogen phosphate (Al ₂ (HPO ₄ ) ₃ ) and / or aluminum dihydrogen phosphate are preferred.

Calcium phosphate, zinc phosphate, titanium phosphate and / or iron phosphate are also preferred.

Calcium hydrogen phosphate, calcium hydrogen phosphate dihydrate, magnesium hydrogen phosphate, titanium hydrogen phosphate (TIHC) and / or zinc hydrogen phosphate are preferred.

Aluminum dihydrogen phosphate, magnesium dihydrogen phosphate, calcium dihydrogen phosphate, zinc dihydrogen phosphate, zinc dihydrogen phosphate dihydrate and / or aluminum dihydrogen phosphate are preferred.

Calcium pyrophosphate, calcium dihydrogen pyrophosphate, magnesium pyrophosphate, zinc pyrophosphate and / or aluminum pyrophosphate are particularly preferred.

These and other similar phosphates may be, for example, by US JM Huber Corporation and are sold under the Safire ^(TM) Products, These include, for example, APP Type II, AMPP, MPP , MPyP, PiPyP. PPaz, include Safire ^(TM) 400, Safire ^(TM) 600, etc. type EDAP.

Yet another phosphates are described, for example, in JP-A-2004204194, DE-A-102007036465 and EP-A-3133112, which are explicitly included in the available component I.

Preferably, the amount ratio of the components C (phosphinate), F (melamine polyphosphate) and I (additive) is such that the latter is the metal phosphate described above, especially if aluminum phosphate is present in the mixture. , Is as follows:
Ingredient C 98-54% by weight,
Ingredient F 33-1% by weight,
Ingredient I 13-1% by weight,
(However, the standard is 100% by weight in total of only these three components).

Yet another additive described above is itself known as an additive to the polyamide composition and can be used alone or in admixture or in the form of a masterbatch.

The above-mentioned components A, B, C, D, E, F, G and optionally H and / or I can be combined in a wide variety to prepare a flame-retardant polyamide composition according to the present invention. For example, the components can be mixed into the polyamide melt at the beginning or end of polycondensation, or in subsequent compounding processes. In addition, there is a processing process in which the individual components are added later. This is especially done in the case of the use of pigment-or additive masterbatch. In addition, particularly powdery components can be optionally incorporated into warm polymer pellets via a drying process using a drum.

Two or more components of the polyamide composition of the present invention can also be combined by mixing before being incorporated into the polyamide matrix. At that time, a conventional mixing device can be used, and the components are mixed in a suitable mixer, for example, at 0 to 300 ° C. for 0.01 to 10 hours.

Granules can also be produced from two or more of the components of the polyamide composition of the present invention, which can continue to be incorporated into the polyamide matrix.

To this end, two or more components of the polyamide composition of the present invention are treated with a granulation aid and / or binder in a suitable mixer or pan-type granulator to obtain granules. be able to.

The initially formed crude product may be dried in a suitable dryer or heat treated to a larger particle size.

In one embodiment, the polyamide composition according to the invention or two or more components thereof can be produced by roll compression.

In one embodiment, the polyamide composition according to the invention or two or more components thereof mixes, extrudes, cuts (or optionally grinds, granulates), and dries (and optionally) the components. By coating), it can be manufactured.

In one embodiment, the polyamide composition of the present invention or two or more components thereof can be produced by spray granulation.

The flame-retardant polymer molding compositions of the present invention are preferably present in granular form, eg as an extrusion or compound. The granules preferably have a cylindrical shape, a spherical shape, a cushion shape, a cubic shape, a rectangular parallelepiped shape, or a prism shape having a circular, elliptical or irregular bottom surface.

The typical length-to-diameter ratio of the granules is 1: 50-50: 1, preferably 1: 5-5: 1.

The granules preferably have a diameter of 0.5 to 15 mm, particularly preferably 2 to 3 mm, and preferably a length of 0.5 to 15 mm, particularly preferably 2 to 5 mm.

The subject of the present invention also relates to a molded article made from the flame-retardant polyamide composition described above, which comprises components A, B, C, D, E, F and G and optionally components H and / or I. ..

The molded article of the present invention can be in any form. Examples of these are fibers, films or moldings that can be obtained from the flame-retardant polyamide molding materials according to the invention by any molding method, particularly injection molding or extrusion.

The flame-retardant polyamide molded product according to the present invention can be produced by any molding method. Examples of these are injection molding, compression, injection foam molding, gas injection molding, blow molding, film molding, calendar molding, laminating or coating at higher temperatures using the flame retardant polyamide molding material described above. Can be mentioned.

The molded product is preferably an injection molded product or an extrusion molded product.

The flame-retardant polyamide compositions according to the invention are suitable for fibers, films and moldings, especially fibers, films and moldings for applications in the electrical and electronic fields.

The present invention preferably includes a plug connector, a current contact component (leakage cutoff) in a power distribution device, a printed circuit board, a sealing material, a power plug, a circuit breaker, a lamp housing, an LED housing, a capacitor housing, and a circuit board. Coil components and ventilators, ground wires, plugs; for plugs, cables, flexible printed circuit boards, housings for mobile phone charging cables, engine covers, or during or for textile coatings, according to the invention. Regarding the use of flame-retardant polyamide compositions.

The present invention is also preferably for electrical / electronic fields, especially printed circuit boards, housings, films, cables, switches, distributors, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, Complexly formed, in the form of components for regulator, memory and sensor components, in the form of widespread components, especially in the form of housing components for control cabinets, and with elaborate geometric shapes. The present invention relates to the use of a flame-retardant polyamide composition according to the present invention for the production of a molded body in the form of a component.

The wall thickness of the molded article of the present invention can typically be up to 10 mm. A molded product having a wall thickness of less than 1.5 mm, more preferably a wall thickness of less than 1 mm, particularly preferably a wall thickness of less than 0.5 mm is particularly suitable.

The present invention will be described with reference to the following examples, but this does not limit the present invention.
1. 1. Ingredients used Commercially available polyamide (ingredient A):
Polyamide 6,6 (PA6,6-GV; melting range of 255~260 ℃): Ultramid ^(R) A27 (BASF)
Polyamide 6 (melting range 217-222 ° C.): Durethan ^(R) B29 (Lanxess)
(Melting range 310-320 ° C.) polyamide 6T / 6,6: Vestamid ^(R) HT plus 1000 (Evonik)
Glass fiber (component B):
Glass fiber PPG HP3610 10 μm diameter, 4.5 mm length (PPG, NL)
Flame Retardant FM 1 (Components C, D and E):
Aluminum salt of diethylphosphinic acid containing 0.9 mol% aluminum ethylbutylphosphinate and 0.5 mol% aluminum ethylphosphonate produced according to Example 3 of US7,420,007B2 Flame Retardant FM 2 (Component C, D and E):
Aluminum salt of diethylphosphonic acid containing 2.7 mol% aluminum ethylbutylphosphinate and 0.8 mol% aluminum ethylphosphonate produced according to Example 4 of US7,420,007B2 Flame Retardant FM 3 (Component C, D and E):
Aluminum salt of diethylphosphinic acid containing 0.5 mol% aluminum ethylbutylphosphinate and 0.05 mol% aluminum ethylphosphonate produced according to the method according to US7,420,007B2 Flame retardant FM 4 (components C, D) And E):
Aluminum salt of diethylphosphinic acid containing 10 mol% aluminum ethylbutylphosphinate and 5 mol% aluminum ethylphosphonate produced according to the method according to US7,420,007B2 Flame Retardant FM 5 (Component C):
Aluminum salt of diethylphosphinic acid produced similar to Example 1 of DE196076335A1 Flame retardant FM 6 (components C and E):
Aluminum salt of diethylphosphinic acid containing 8.8 mol% aluminum ethylphosphonate Flame retardant FM 7 (component H):
Aluminum salt of phosphonic acid prepared according to Example 1 of DE1020111120218A1 Flame retardant FM 8 (Component F):
Melamine polyphosphate flame retardant FM 9 (not according to the present invention) prepared according to the example of WO2000 / 002869A1:
A melamine polyphosphate flame retardant FM 10 having an average degree of condensation of 18, manufactured similar to WO2000 / 002869A1 (not according to the present invention):
Red phosphorus (Exolit ^(R) RP 607, Clariant Produkte (Deutschland ) GmbH)
Flame Retardant FM 11 (not according to the present invention):
80% antimony trioxide masterbatch in PA6 and (Campine Company), 25%: 75% brominated polystyrene mixed in a ratio (Saytex ^(R) HP 3010, Albemarle Corporation)
Black colorant G1 (component G)
Carbon black ^{(Printex (registered trademark)} XE2, Evonik)
Black colorant G2 (component G)
Nigrosin CI Solvent Black 7 (Nylon BAP, Lanxess, Leverkusen, Germany 2. Manufacture, processing and testing of flame retardant polyamide molding material The flame retardant component is mixed with the colorant in the ratio shown in the table and extruded by a biaxial screw. Knead to PA6,6 at a temperature of 260-310 ° C, PA6 at 250-275 ° C, or PA6T / 6,6 at 310-330 ° C via the side feeder of the machine (Leverkutz ZSE 27 / 44D type). The glass fibers were added via a second side feeder. The homogenized polymer strands were taken up, cooled in a water bath and subsequently granulated.

After being sufficiently dried, the molding material is processed into test pieces in an injection molding machine (Arburg 320 C Allrounder type) at a material temperature of 250 to 320 ° C., and flame retardancy is tested based on the UL94 test (Underwriter Laboratories). Classified. In addition to the classification, the residual flame time was also shown.

The comparative tracking index of articles was determined according to the International Electrotechnical Commission standard IEC-60112 / 3.

The glow wire flammability index (GWIT-Index) was determined according to the IEC-60695-2-12 standard.

The color of the part was visually evaluated. Means: 1 = deep black, 2 = deep black with a slight reddish color, 3 = deep black with a clear reddish color.

All tests in each series were performed under the same conditions (eg, temperature program, screw shape and injection parameters) for comparability unless otherwise stated.

Examples 1A to 5C and Comparative Examples V1A to V5B using PAs 6 and 6.

The results of tests using PA6, 6 molding materials are listed in the examples shown in the table below. All amounts are expressed as% by weight and are based on polyamide molding materials including flame retardants, additives and reinforcements.

例１Ａ〜５Ｃの本発明によるポリアミド組成物は、０．４ｍｍで燃焼性等級ＵＬ９４ Ｖ−０を達成し、同時にＣＴＩ ６００ボルトおよびＧＷＦＩ ９６０℃を有し、赤みを帯びることなく深い黒色の着色を示す成形材料である。例５Ａ、５Ｂおよび５Ｃにおける成分Ｈの添加は、低減された残炎時間によって示される難燃性のさらなる改善をもたらす。

The polyamide compositions of Examples 1A-5C according to the invention achieved flammability grade UL94 V-0 at 0.4 mm, while at the same time having a CTI of 600 volts and a GWFI of 960 ° C, with a deep black tint without redness. It is a molding material shown. Addition of component H in Examples 5A, 5B and 5C results in a further improvement in flame retardancy as indicated by the reduced residual flame time.

Omission of component D in Comparative Examples V1A and V1B resulted in a decrease in CTI values compared to Examples 1A-4B, in addition to an increase in afterglow time.

In Comparative Examples V2A and V2B, when the component F was replaced with a component having a lower degree of condensation, the polyamide strands foamed during production, and the measurement could not be performed.

In Comparative Examples V3a and V3B, when red phosphorus was used instead of the components C, D and E, a clear redness was produced in the color of the molded product.

Omission of components D and E in Comparative Examples V4A and V4B resulted in a decrease in CTI values compared to Examples 1A-4B, in addition to an increase in residual flame time.

In Comparative Examples V5a and V5B, the use of brominated polystyrene / antimony trioxide in place of components C, D and E resulted in a clear redness in the color of the part and a decrease in CTI value.

Examples 6A to 10B and Comparative Examples V6A to V10B using PA6, 6 / PA6
The results of tests using PA6 / PA6,6 molding materials are listed in the examples shown in the table below. All amounts are expressed as% by weight and are based on polyamide molding materials including flame retardants, additives and reinforcements.

例６Ａ〜１０Ｂの本発明によるポリアミド組成物は、０．４ｍｍで燃焼性等級ＵＬ９４ Ｖ−０を達成し、同時にＣＴＩ ６００ボルトおよびＧＷＦＩ ９６０℃を有し、赤みを帯びることなく深い黒色の着色を示す成形材料である。例１０Ａおよび１０Ｂにおける成分Ｈの添加は、低減された残炎時間によって示される難燃性のさらなる改善をもたらす。

The polyamide compositions of Examples 6A-10B according to the invention achieved flammability grade UL94 V-0 at 0.4 mm, while at the same time having a CTI of 600 volts and a GWFI of 960 ° C, with a deep black tint without redness. It is a molding material shown. The addition of component H in Examples 10A and 10B results in a further improvement in flame retardancy indicated by the reduced residual flame time.

Omission of component D in Comparative Examples V6A and V6B resulted in a reduction in CTI values compared to Examples 6A-9B, in addition to an increase in afterglow time.

In Comparative Examples V7A and V7B, when the component F was replaced with a component having a lower degree of condensation, the polyamide strands foamed during production, and the measurement could not be performed.

In Comparative Examples V8a and V8B, when red phosphorus was used instead of the components C, D and E, a clear redness was produced in the color of the molded product.

Omission of components D and E in Comparative Examples V9A and V9B resulted in a decrease in CTI values compared to Examples 6A-9B, in addition to an increase in the residual flame time.

In Comparative Examples V10a and V10B, when brominated polystyrene / antimony trioxide was used instead of the components C, D and E, a clear redness was produced in the color of the molded product and the CTI value was reduced.

Comparative Examples V11 to V18 using PA6T / 6,6
The results of tests using PA6T / 6,6 molding materials are listed in the examples shown in the table below. All amounts are expressed as% by weight and are based on polyamide molding materials including flame retardants, additives and reinforcements.

ＰＡ成形材料が加工不能であることが判明したので、比較例Ｖ１１〜Ｖ１８のＰＡ成形材料のいずれからも試験片を製造することはできなかった。ポリアミドストランドが製造中に発泡し、測定に適した試験片は製造できなかった。

Since it was found that the PA molding material could not be processed, a test piece could not be produced from any of the PA molding materials of Comparative Examples V11 to V18. Polyamide strands foamed during production, and test pieces suitable for measurement could not be produced.

Comparative Examples V19 to V23 Using PA6, 6
From Table 4, it can be seen that a polyamide composition having the characteristics of V-0, GWFI 960, and CTI 600 and a deep black color can be produced only when the combination of the flame retardants according to the present invention is used. V-0 can be achieved by using melamine polyphosphate alone or by using antimony trioxide and polystyrene brominated, but not deep black coloring.

Claims (20)

Flame-retardant polyamide composition including:
-As component A, a polyamide having a melting point of 290 ° C or lower,
-As component B, filler and / or reinforcement,
-As component C, the phosphinate of formula (I)

[In the formula, R ₁ and R ₂ represent ethyl and
M is Al, Fe, TiO _p or Zn,
m represents 2-3, and p = (4-m) / 2],
-A group of Al-, Fe-, TiO _p- or Zn salts of ethylbutylphosphinic acid, dibutylphosphinic acid, ethylhexylphosphinic acid, butylhexylphosphinic acid and / or dihexylphosphinic acid as component D. Compounds selected from,
-As component E, the phosphonate of formula II

[In the formula, R ₃ represents ethyl and
Met is Al, Fe, TiO _q or Zn.
n represents 2-3, and q = (4-n) / 2],
-As component F, melamine polyphosphate having an average degree of condensation of 2 to 200, and-as component G, a black colorant. The flame-retardant polyamide composition according to claim 1, wherein M and Met represent Al, m and n are 3, and component D is an aluminum salt. -The ratio of component A is 25 to 95% by weight,
-The ratio of component B is 1 to 45% by weight,
-The ratio of component C is 1 to 35% by weight,
-The ratio of component D is 0.01 to 3% by weight.
-The ratio of component E is 0.001 to 1% by weight.
-The proportion of component F is 1 to 25% by weight, and-the proportion of component G is 0.01 to 20% by weight.
The flame-retardant polyamide composition according to claim 1 or 2, wherein the percentage display is based on the total amount of the polyamide composition. -The ratio of component A is 25 to 75% by weight,
-The ratio of component B is 20-40% by weight,
-The ratio of component C is 5 to 20% by weight,
-The ratio of component D is 0.05 to 1.5% by weight.
-The ratio of component E is 0.01 to 0.6% by weight.
The flame-retardant polyamide composition according to claim 3, wherein the proportion of the component F is 2 to 10% by weight, and the proportion of the component G is 0.1 to 8% by weight. The flame-retardant polyamide composition according to any one of claims 1 to 4, further comprising an inorganic phosphonate as another component H. The inorganic phosphonate is of formula (III)

[In the formulas, Me, Fe, a _TiO r, Zn or especially Al,,
o represents 2-3, and r = (4-o) / 2]
The compound of the formula III is present in an amount of 0.005 to 10% by weight, particularly 0.02 to 5% by weight, based on the total amount of the polyamide composition. The flame-retardant polyamide composition according to claim 5. The flame-retardant polyamide composition according to any one of claims 1 to 6, which has a comparative tracking index of 500 volts or more measured according to the International Electrotechnical Commission standard IEC-60112 / 3. The flame-retardant polyamide composition according to any one of claims 1 to 7, wherein the evaluation of V0 is achieved according to UL-94 with a thickness of 3.2 mm to 0.4 mm. The flame retardancy according to any one of claims 1 to 8, characterized by having a glow wire flammability index of at least 960 ° C. according to IEC-60695-2-12 with a thickness of 0.75 to 3 mm. Polyamide composition. One of claims 1 to 9, wherein the component A is one or more polyamides selected from the group consisting of PA6, PA6,6, PA4,6, PA12, PA6,10. The flame-retardant polyamide composition described. The flame-retardant polyamide composition according to claim 10, wherein the component A is a polyamide 6, 6 or a polymer mixture of the polyamides 6, 6 and the polyamide 6. The flame-retardant polyamide composition according to claim 11, wherein the component A comprises at least 75% by weight of the polyamides 6 and 6 and up to 25% by weight of the polyamide 6. The flame-retardant polyamide composition according to any one of claims 1 to 12, wherein glass fiber is used as the component B. The invention according to any one of claims 1 to 13, wherein the components C, D, E and F are present in a particulate form, and the median particle size d ₅₀ of these components is 1 to 100 μm. Flame-retardant polyamide composition. The flame-retardant polyamide composition according to any one of claims 1 to 14, wherein the melamine polyphosphate has an average degree of condensation of 2 to 100. The flame-retardant polyamide composition according to any one of claims 1 to 15, wherein the melamine polyphosphate has a decomposition temperature of 320 ° C. or higher. The component G is a group consisting of carbon black, graphite, graphene, niglocin, bone charcoal, and black coloring pigments, or a combination of red to yellow pigments which are complementary colors and green, blue or purple pigments, or a compound thereof. The flame-retardant polyamide composition according to any one of claims 1 to 16, characterized in that it is selected from one or more mixtures. The flame-retardant polyamide composition according to claim 17, wherein the component G is carbon black or niglocin. The component I contains yet another additive, wherein the other additive is an antioxidant, a UV stabilizer, a gamma ray stabilizer, a hydrolysis stabilizer, a co-stabilizer for an antioxidant, an antistatic agent. , Emulsifiers, nucleating agents, softening agents, processing aids, impact resistance improvers, dyes different from component G, pigments different from component G and / or different from components C, D, E, F and H The flame-retardant polyamide composition according to any one of claims 1 to 18, characterized in that it is selected from the group consisting of different flame retardants. Use of the polyamide composition according to any one of claims 1-19 for the production of fibers, films and moldings, especially fibers, films and moldings for use in the electrical and electronic fields.